Detergents containing imidazoline lactates



Patented Feb. 16, 1954 DETERGENTS CONTAINING IMIDAZOLINE LACTATES HymanW. Zussman an Providence, R. I., assig Company, Cranston,

Rhode Island 41 Robert L. Bernstein, nors to Alrose Chemical R. L, acorporation of No Drawing. Application December 23, 1949, Serial No.134,863

12 Claims. (01. 252-153) This invention relates to surface active agentsof the cation-active type, and more particularly to the lactate salts ofcertain substituted imidazolines. It also relates to surface activecompositions for use in organic liq'uids. The primary use of the lactatesalt of the substituted imidazcline of the present invention is in thepreparation of cleaning fluids, particularly for dry cleaning ofgarments and other textile fabrics. Although this is the primarycommercial use, they can be employed with successful results in thecleaning of metals and other solid surfaces where an organic solvent isemployed, to free them of films, coatings or deposits including grease,oil and attached extraneous solid matter, etc.

1 .The cation-active type surface active agents of the present inventionhave. detergent and sludge dispersing properties and; because .of which,when used in fuel oil and lubricants are effective in dispersing sludgeand varnish deposits in engines.

In the dry cleaning of textiles, e. g. finished materials composed ofcotton, wool, natural silk,

cellulose esters, regenerated cellulose, nylon or other synthetic fibersor filaments, and mixtures of these recited fibers or filaments, it hasbeen a common practice to employ a volatile organic solvent such asStoddard solvent, a poly-chlor hydrocarbon, benzene or white spirit inwhich is dissolved a soap, for instance potassium or triethanol ammoniumoleate, and if desired Water. And dry cleaning fluids which contain aquaternary ammonium salt, polyethylene glycol esters of fattyacids,polyethyleneoxide ethers of higher alcohols or phenols and ammoniumsalts of alkyl aryl sulfonates and other surface active agents have beenutilized in dry cleaning and related branches ofliquid detergency. .Manyof these aforesaid mentioned surface active agents are not, however,very effective in improving the removal of solid soil. Many of them dolittle more than permitthe inclusion of water in the solvent, which isrecognized as possessing two advantages: reducing the build-up of staticelectricity and increasing the removal of water-soluble stains in thecleaning processes.

1 Stoddard solvent is described in a U. S. Bureau of Standardspublication Stoddard Solvent CS3-40." designated as petroleum distillatewith a flash point not lower than 100 F. when tested in the Tag closedheater. The distillation range when a sample is distilled in a certainspecified apparatus is that not more than 50% shall be recovered in thereceiver when the thermometer reads 3 B1, and the end point peratureshall not be higher than 410 F.

of maximum distillation tein- We have discovered that the lactate saltsof substituted imidazolines of the type described below are surfaceactive agents which when incorporated in organic solvents produceunusually effective liquid detergents. They surpassed suchcationic-active types of surface active agents as fatty acid amides,aliphatic primary-, secondary-, and tertiary amines, quaternary ammoniumcompounds, oxazolines and other imidazolines when formed intocorresponding dry cleaning detergents.

The lactate salt of imidazolines substituted in the 2-position by asaturated aliphatic hydrocarbon of seventeen carbon atoms, particularlyby the alkyl group we have found possess very pronounced surface activeproperties. Where this substituent has less than seventeen (17) carbonatoms the eifective'ness is less as a detergent in organicli-quids.Salts other than the lactate, which wereiinvestigated; including thecaprate, oleate, acetate, hydr'oxyacetate, gluconate and tartrate werefar less'efiectivethan the lactate.

The lactate salts of Z-heptadecyl imidazolines in-" corporated in verysmall quantities in the conventional solvents of the dry cleaningindustry are unusually eifective liquid detergents.

. Its formula is:

N-CH2 v cums-c .CHaCH(OH)COOH NIH-CH2 It can be-d'efinitelyasserted'that the 2 -position substituted imidazolines in the form of alactate salt, the substituent of which ispreferably an alkyl radical ofseventeen carbon atoms, when incorporated .in such volatile, solventsas.

Stoddard solvent, perchloroethylene,trichloro ethylene or carbontetrachloride, produced-a cleaning fluid superior to either theserespective solvents alone or to such solvents containing such othercationic agents as'mentioned supra. It has also been found that thistype of imidazoline salt substituted also in the l-position by such'groups as hydroxylethyl, aminoethyl, benzyl and ethyl'benzene was alsoeffective when incorporated in the above mentioned conventionahvolatileorganic solvents. Of these substances, the lactate salt ofl-hydroxylethyl 2- heptadecyl imidazoline is preferred. Its formula is:

N-om

Cl'I IMiO ..CH3CH(OH)COOH v N-CH:

HO-CzHa The compounds of the present invention mentioned supra may beused as additives in any of the dry cleaning solvents commonly in usesuch as those mentioned by Brown in the Journal of the SocietyoLDyersand Colourists- 1933, page 42. Since-very small; quantities of;any of these substances is all that is usually necessary, the cleaningprocesses employing the same are com nomical. This does not preclude theuse of larger quantities. The amount for optimumresultscanl bedetermined for any one compound, solvent and textile goods by a fewtrialsa The preferred BmDOdimCHtOfithiSiIIVfiIltiOMfislates to detergentcompositionsiwliichaeontain the lactate salt of l-hydroxylethylZ-heptadecyl imidazoline. In the dry cleaning. pmcessesthe. fluids wouldordinarily be those conventionally employed and in the metal cleaningprocesses those customarily employed in that branch of detergency.

The;effectiveness=,ofi this oationimsuriacez active agent. as; relatesto; dintzremovalifrcm fabrics; will: heaproven. The;-testr'employedwamthe measurement of reflectance ofaswatches: of. thesciledrcels lulose; acetate. fabric: and: the same soiled fabric;cleaned! by various dry; cleaning; fiuidsz:amhotnevolt-reflectometen'moderfilOawas-usedl Thi'semat chinesendsabeannoficonstantl intensity ofilight' against-the swatch;vThe:principle ofioperationsiss that a. centaimpercentage: or. this;light: is: re-

flected back and picked up by azphotoelectriczceil; With; aperfect-reflecting;- sur;face;. the reflectance will? be 100%; or: 100,;leaving. off the; percentage. 5:. periectlyrblacle. body: will: have: areflectance of: ZCIIDJDEIQCBBI'I, 12.6.0).

The: swatches of: soiled: fabric were: cleaned, identical: conditions.The. solvent: in: each cleaning: operatiom im the: table: was? pen--chlomethylenez-ami there werafiveatestsinzwhicin 012.5%; of thezvarious' surface? active materialslisted this; table: was present in:vthe: solventr. 'llhmreflectanceivaluesfm' each appear: imthe-tahlei,

Nature of Fhbrid'I i-eatment Reflectance Check, i. e. Soiled Fabric (notreatment). 6 Solvent alone l9 Solvent Naccolenc 30 Solventsteary1amine.. 32 Solvent Hydroxyethyl 01eamide 33 Solvent Span 3 33'Naccoleuc" is a trademark prodiictunderstoodito. beamam: moniunrselt ofan alkyl-aryl sulionatm From this: table: it; iss quite; apparent;that", the reflectance ot. thisv imidazolinee derivative solventtreated; swatch; is, iarxinr. excess of;- any others; meaning. thatthere-sis: lesszresidual dint il iIlZthBFffibfi-C;Comparable:resultsaliasrealsotbeen ohtainedemploying"Stoddardssolventi"insteadlci the.-perchloroethylene;above:whereimsuchzvariect fabrics as rayon; wooliand cottonzhave been:suhejectedlto. thisreflectanceatest, ,each: demonstrating: the: tablethe: superiors-soil removing; cat Danity:of;thislimidazolinezderivative;

Tlherpowerfulldispersingr andlsuspending: action: of this imidazolinederivative in dry cleaning sol-- vents has in a qualitative, yeteffective way been demonstrated asvfollows:

Two pieces of white cotton fabric were well marked with lipstick;oneapiece was put into a jar of pure solvent and the other intathe sameor (ill orange and hairdressing stains from garments,

as well as loosen glue and other spots even when usedzwithoutr'moistureeWith moisture such solutipnsi areemore: eflfcient in removing the morewater-soluble stains, including perspiration.

However; watersolutions alone are never employed. A; solution: of thelactate salt of 2- heptadecyl imidazoline in Stoddard solvent,perchloroethylene or other common organic volatile solvents; when usedwithout moisture will not cause shrinkage or wrinkling. Such solutionswilhclsarrknittedzhlcosely woven and softi wool'ens without? changeeindimensions. They are excel'-= lent: detergents for:- textile materials:which t'end to faderinr. cleaning such as draperies; and seat covers. Aslittle asatwo orthree ouncesof this: salt; per hundred: pounds: ofgarments employed at concentrations=.:irr organic scivents'-of-; & toV4?" 0t L%. or thereaboutswill step up' di'rt removal capacity'ofpetroleum solvent at least- 25 and cffStoddardsolVent!approximately-40%;

2'-hepta'decyl' imidazolin'e lactate and such 1 positionsubstitutedxlerivativesas=the l -liydroxyw ethyl hav limited: solubility11mm; of the or genie-solvents.- Theysare; therefore; impractlc e:somewhat difficult: to incorporate in the'oonve'n tional dry cleaningsolvents: It has been:- found advantageous 'to" liquety'thESBFlECtHtESEIfS, which are'in; their" pure form waxy 'solid's; by*the addi r tion ofvariousoil-soluhilizing poiyalcohol esters of; higherfatty acids; petroleumsulfonates' and other: oili-sclubilizingsurfaceactive agents; at the same time these lactate salts are by this:made miscible with: the organic" solvent. Many ofithesesolubilimngagents also improve thewater' emulsifying action of the detergent; TheMore-- said. polyhydric; esters= can be those of glycerol, ethyleneglycol, di'propylene' glycol; propylene glycol, polyethylene'glycoh etc;

While:.it has? been= noted that some of these oil'esoluhilizingagents;suchas" polyethylene gly'- coir 2005* monolaureat'e polyethyleneglycor300 monolaurate or polyethylene glycol 400 -mono; (nearehave: a:detrimental effect on the deter gency or" the. lactate saltoffl-hydrcxyethyl 2- heptadecyl: imidazoline; several other oil-sol'ubilizing; agents; while themselves rather'p'oor dry cleaning detergents;exhibit; a marked synergistic; effects. when: mixedtwith: thisi'midazoline salt: Thus; while; 012.5%. of: dinropyleneglyccl m'onool'eatezincreasesxthe i'efiect'ance of standard?rayon fabric commie-221mperchloroethylene, and a 0.25%; solutioinoithenlactat'eof-ll-hydroxyethyl' zj-heptade'cyh imidazoline alone. increases thereflectancatov 4e; a1.0.25;%':solution of l z'li 1:2 and Zilz mixture:of the. fornrer'with the latter' eachproduce; reflectance of? as to:4-37 employing thesame: solvent: in; each: comparative test;-

It may also be desirabletovadct'small quanti ties of isopropanol,ethyleneglycol, carbitols i: e:. diethyleneglycoiemonoethyl? ether;or=liexyleneglycols etc. as. coupling agents to= improve; the, physicalstability: or the 2 hept'adecyll. imid'irst; numbers; 20121 3002 and.400:. mean; that, the; polyethylenezglycolffrom'whichVtheseirespectiveaestermweree aside hadthemoicculan-vreight;correspomiingtolthatmu n azoline lactate concentratesas articles of commerce. By coupling agents is meant a chemicalsubstance which possesses the property of solubilizing or dispersing acompound that is normally only partially soluble in a solvent, which maybe either an aqueous or a non-aqueous type. In the absence of the secondadditive this first substance would settle out of solution due to itslimited solubility. The term "coupling agent is broader thanoil-solubilizing agent which is restricted to promoting solubility ofthe compound in the Water-immiscible organic solvents.

The following examples are given to illustrate the invention but do notlimit the invention. The parts are by weight.

Example 1 Parts Lactate salt of l-hydroxyethyl 2-heptadecyl imidazoline40 Dipropylene glycol mono-oleate Glycerol mono-oleate Ethylene glycolmonobutyl ether 5 One quart per hundred pounds of garments of a drystock solution prepared by thoroughly dispersing one part of the abovematerial into ten parts of petroleum solvent will be found to increasethe coil removal efficiency of petroleum solvent at least while enablingcomplete or at least partial removal in the dry cleaning machine of suchstains as lipstick, paint, and ink and at the same time will preventsoil redeposition.

Two quarts per hundred pounds of garments of a wet stock emulsionprepared by emulsifying one part of water with one part of the above drystock solution will be found to increase the soil removal efficiency ofpetroleum solvent while removing such stains as coffee, fruit juices,gravy, etc. in the dry cleaning wheel in addition to removing the stainsby the dry stock solution alone, as mentioned supra. As in the case ofdry stock solution, soil redeposition is prevented.

Both the dry stock solution and the wet stock emulsion will increase thenumber of silk pass ups at least and at the same time decrease thenumber of re-runs which are necessary. In ad dition, the wet stockemulsion will increasereversible pass ups 80% or better while keepingthe amount of Wet cleanin down to a maximum of 10%.

Example 2 Parts Lactate salt of l-hydroxyethyl 2-heptadecyl imidazoline30 Nonisol 200 25 Glycerol mono-cleats 40 Ethylene glycol monobutylether 5 Four fifths of a pint per 30 pounds of garments of a dry stocksolution prepared by thoroughly dispersing one part of the abovematerial into ten parts of synthetic solvent (trichlorethylene) it willbe found to be at least double the soil removal eiiiciency of thissolvent while enabling the complete or at least partial removal in thedry cleaning machine of such stains as lipstick, paint, and ink. At thesame time the use of this dry stock solution will prevent soilredeposltion.

One pint per 30 pounds of garments of a wet stock emulsion prepared byemulsifying four parts of water with eleven parts of this dry stocksolution using chlorinated solvent will do all that the dry stocksolution will do and, in addition, will remove such stains as cofiee,paint, and ink plus the usual soft and sweet stains.

Both the dry stock and the wet stock emulsion will be found to increasethe number of silk pass ups while decreasing the number of rerunsnecessary. In addition, the wet stock emulsion will increase reversiblepass ups or better and will keep the amount of wet cleaning needed to amaximum of 10%.

Nonisol 200 is a trade-mark product of the non-ionic type of the AlroseChemical Company, Cranston, Rhode Island.

Example 3 Parts Lactate salt of 2 heptadecyl imidazoline 20 Petroleumsolvent 80 One quart of the above mixture per pounds of garments will befound to increase the soil removal efiiciency of petroleum solvent,prevent soil re-deposition, remove many stains not affected by thesolvent alone and when used in conjunction with water will remove commonwater soluble stains.

One gallon of such formulations supra as exemplified (based upon thenon-inclusion of the solvent) will ordinarily clean 4000 to 6000 lbs. ofclothes. It can be added directly to the wheel. When employed in a drycondition, only one or two ounces per fifty pounds of clothes issufficient. A stock solution may be prepared from 1 quart of theformulation from Examples 1, 2 or 3 and 20 quarts (5 gallons) ofsolvent. As a moisturized detergent one quart of one of theformulations, 7 quarts of solvent and one quart of water is suggested. Aratio of 1.5 pints of this moisturized stock detergent solution perfifty pounds of garments (light or dark woolens, silks, whites) isusually ample-to secure excellent cleaning results. More moisture may beused as desired.

For prespotting, a higher ratio of the formula tion to solvent isemployed, such as one part of the formulation to 3-4 parts of solvent,with or without moisture emulsified in it; this makes a powerfulprespotting preparation. Heavily moisturized prespotting preparationswith such salts as these imidazoline derivatives therein may be used incleaning plants employing carbon tetrachloride to derive the benefits ofmoisturized cleaning but without putting moisture into the dry cleaningmachines.

Some of the advantages in employing lactate salts of imidazolinesubstituted in the 2-position by an alkyl group of seventeen carbonatoms will now be summarized. The flash point of the lactate salt ofboth the 2-heptadecyl imidazoline and the l-hydroxyethyl Z-heptadecylimidazoline is 235 C. It may be used with or without moisture as desiredin organic solvent detergency, depending upon whether the presence orabsence of moisture is the most efficient or whether water will causeshrinkage. It prevents soil re-deposition in dry cleaning. It secures animprovement in dry cleaning quality, reducing spotting and wet cleaningcosts and giving better cleaned garments. Silk pass-ups 7 in plantsusing it have doubled, and pass-ups on reversibles have been 80% andhigher. In dry cleaning its use produces garments with a soft. freshfeel and the garments are easy to press and finish. More- 'A pass-up isa garment which does not have to be put upon the spotters board forfurther cleaning because of spots or stalns. A reversible pass-up isunderstood as any garment usually made of cotton which is worn as araincoat or light overcoat.

over it; leaves-.110: odorruponzthe garments; Used with organicsolvents. itzbuilds? up no filtenprese SHIBWIRDTOlOIIEEdJlSE. Itmaybe-usedawith any dry cle'aningi equipment. and with any filter aid.And' in the recoveryof; solvent it. does not foam hr the! still; It? isnoncorrosive: to metals-.- and actuallyreduces the danger ofcorrosionwhen carbon tetrachloride: iszem'ployed;

In cleaningi solid. surfaces higherboiling; sol!- vents= may be used.instead. of these customarily employedfin the: dry. cleaning industry;But the cationic-active surface: active. agents of the present inventionmay. be employed with such organic liquids with similar effectiveness.In fact it finds service in organic.liquiddetergency in its many diverseindustrialfields'.

Moreover because of its surface active'propertiesfi the" lactate salts'of the? seventeen. carbon atoms saturated aliphatic hydrocarbom,substituted" imidazolin'esand the 1-position substituted derivatives ofthe type indicated hereinalso car he used to disperse sludge in"- fuel.oil and l'ubricantsz While the invention has been describediwithreference to particular embodiments-2 and: specific examples; it'- isnotintended: that: our: invention shall be limited to such, exceptashereinaft'er described inthe'appended' claims. lttwill be reali'zed bythose skilled in' the: arts" that various changes may be made in the:composition andformulation of the detergents: and cleaning agents;

We claimasourinvention:

l.- A surf ace active 3 compound? whichr. 15131181128? tate salt of theiinidazoline substituted; in the' 2-position'-by an alliyl group ofseventeenicarbon atoms, but whose 4 an'd 5 positions: are: unsubstit'uted.

2? A surface" active 6-. A' surface aptive=composition=comprising thelactatesa'lt of an imidazolinewhich'is suhstituted' ih"the'2'-position'by an alkyl group ofseventeen' carbon. atoms and" is substituted in theI-p'osition by the'hydroxyethyl group, but whose 4 and 5 positionsareunsubstituted, and a polyhydri'c alcohol ester of" a higherfattyacid; this last mentioned"componentbeing present in'an' amount'sufficient to liquify the former and render it miscible with the chosenliquid selected from the group consisting of hydrocarbons andpolychlorinated hydrocarbons.

75 A surface active composition comprising: a

compound" whichv is. the v lactatesal't of the-imidazo'lihe substit'utedinzthe lactate-salt. of. an. imidazoline. which. is' substl tuted in=the2aposition .by analkyLgroun-of sevem teen carbon. atoms. butwhose- 4and. 5 positions areunsubstituted, admixed with-azdipropyleneglycoliester of. a higher fatty'acid, thelast component. being presentin. an amount suffie cientto-liquefyrthe. former. and render it misciblewith .thechosen liquid solvent selectedfrom the group consisting ofhydrocarbons and polychlo. rinated hydrocarbons;

8. A surface. activecomposition comprising. the lactatesaltfof.2-heptadecyl imidazoline. admixed. with a dipropylene glycol ester of ahigher fattyacid, the last. component. being present. in: an amountsufficient to liquefy the former and render it miscible with thechosenliquidsolvent selected from the group consisting of hydrocarbonsand polychlorinated hydrocarbons.

9'; A surface active composition comprising the lactate salt ofl-hydroxyethyl 2-heptadecyl* imidazolinelactate admixed with adipropylene glycol'esterof a higher fatty acid, the last com-'ponentbeing present in an amount suficient-to' liquefy the former andrender it miscible withthe chosen liquid solvent selected from the'groupconsisting' of hydrocarbons and polychlorinatedrhydrocarbons.

10. A' liquid detergent comprisingv a volatile organic liquid solvent.selected from the group consisting of hydrocarbons and. polychlorinatedhydrocarbons containing therein alactate salt of an. imidazoline whichis substituted in the-2.- position by analkyl. group of seventeen.carbon atoms out whose i and 5 positions are unsubstituted, the saidlactate-Salton the imidazolinebeing present in the liquid detergentirran amount of not over a few per cent based on the:concen trationdnthe. organic liquid solvent.

11. A liquid. detergent. comprising a volatile. organic liquidvsolventselectedfrom the. group consisting of hydrocarbons andpolychlorinated.

hydrocarbons; containing therein a lactate-salt of. animidazoline whichis substituted in. the 2 position by an alkyl group of seventeen carbonatoms but whose 4 and 5. positions-are unsubstituted andis-substituted.in the l-positionby. a member of the group. consisting. of hydroxyl.-ethyl, aminoethyl,. benzyl. and ethyl. hexyl, the said lactate :salt of.theimidazoline. being present in .the liquid. detergent in an amount of.not over. a. few. per cent. based. on. the: concentration. in theorganic liquid solvent.

12. A surface active composition comprising the lactate salt ofl-hy'di'oxylethyl Z-heptadecyl imidazoline and dipropylene glycolmono-oleate, the ratio oftheformer to'the latter being 221-122;

- HYMAN'W. ZUSSMAN.

ROBERT L. BERNSTEIN.

References. Cited. in; the. file of this patent UNITED.- STATES. PATENTSNumber Name Date 2,155, 877' Waldmann et a1. Apr. 25, 1939' 2,194,906Krzikalla Mar. 26, 1940 2,211,001 Chwala Aug. 3, 1910 2,267,965 WilsonDec; 30; 1941* 2 ,317,112 Pings Apr; 20, 1943

1. A SURFACE ACTIVE COMPOUND WHICH IS THE LACTATE SALT OF THEIMIDAZOLINE SUBSTITUTED IN THE 2-POSITION BY AN ALKYL GROUP OF SEVENTEENCARBON ATOMS, BUT WHOSE 4 AND 5 POSITIONS ARE UNSUBSTITUTED.
 6. ASURFACE ACTIVE COMPOSITION COMPRISING THE LACTATE SALT OF AN IMIDAZOLINEWHICH IS SUBSTITUTED IN THE 2-POSITION BY AN ALKYL GROUP OF SEVENTEENCARBON ATOMS AND IS SUBSTITUTED IN THE 1-POSITION BY THE HYDROXYETHYLGROUP, BUT WHOSE 4 AND 5 POSITIONS ARE UNSUBSTITUTED, AND A POLYHYDRICALCOHOL ESTER OF A HIGHER FATTY ACID, THIS LAST MENTIONED COMPONENTBEING PRESENT IN AN AMOUNT SUFFICIENT TO LIQUIFY THE FORMER AND RENDERIT MISCIBLE WITH THE CHOSEN LIQUID SELECTED FROM THE GROUP CONSISTING OFHYDROCARBONS AND POLYCHLORINATED HYDROCARBONS.